JPS6077961A - Permanent magnet material and its manufacture - Google Patents

Abstract

PURPOSE:To manufacture a permanent magnet material having excellent performance at low cost by molding and sintering the powder of an alloy consisting basically of Fe, B and rare earth elements and containing specific metallic materials. and thereafter heat-treating the sintered body. CONSTITUTION:The alloy consisting of by atomic percentage 8-30% at least one kind of rare earth element containing Y, 2-28% B, <50% Co, at least one kind of the following M1, M2 and the balance Fe is manufactured. Wherein, M1 and M2 are the elements having the amount shown in the tables I , II and the total amount of the two are regulated to the value not more than the maximum value among contained % in the elements shown by M1 and M2. The alloy having this composition is crushed so that the average grain size is regulated to 0.3-80mum and is pressurized and molded, thereafter is sintered at 900-1,200 deg.C in a nonoxidizing or reducing atmosphere. Following this, said alloy is subjected to aging treatment at the temperature within the range of 350 deg.C- the sintering temperature in a vacuum or gaseous inactive atmosphere for 5min-70hr. A permanent magnetic material having excellent performance is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel rare earth magnet, which is based on FeBR, contains an additive element M, does not necessarily require rare rare earth metals such as Sm, and is rich in resources and has few uses.
The present invention relates to a high-performance permanent magnet material whose main components are light rare earth elements such as d and Pr, and a method for manufacturing the same.

Permanent magnetic materials are one of the extremely important electrical and electronic materials used in a wide range of fields, from various household appliances to peripheral terminal equipment for large computers. In recent years, with the demand for smaller size and higher efficiency of electrical equipment, permanent magnet materials are becoming more and more high-performance.In addition, in practical applications, they are used in applications such as magnetic couplings for motor generators, etc. that can handle extremely large reverse magnetic fields. Magnet materials with high coercive force are also being sought for in many such applications.

Representative permanent magnets currently in use are alnico, hard ferrite, and rare earth cobalt magnets. A recent permanent magnet that satisfies high magnetic properties is an earth cobalt magnet.

However, rare earth cobalt magnets are very expensive because they require Sm, which is a rare resource, and use a large amount of CO, which is in unstable supply.

In order for rare earth magnets to be used in a wider range of fields and in large quantities, they must not contain large amounts of expensive cobalt and instead be made mainly of light rare earths, which are found in large amounts in ores as rare class 2 metals. is necessary. RFez-based compounds (where R is at least one rare earth metal) have been proposed as an attempt to develop such permanent magnet materials. Clark (A
, E, C1ark) is amorphous TbFe2 obtained by sputtering at 4.2° and 29.5 MGOe.
+7) It has a z Nerky product and is heated to 300 to 500°C.
It was found that when heat treated at room temperature, the coercive force was 3.4 kOe and the maximum energy product was 78 GOe. A similar study was conducted on SmFe2 at 9.2M at 77°.
It has been reported that it exhibits GOe.

But were all of these created by sputtering? 1 [It is a membrane and is not a magnet that can be used in general speakers or motors. It has also been reported that a ribbon produced by ultra-quenching a PrFe-based alloy exhibits a high coercive force of 2.8 kOe. Furthermore, Kuhn et al. (Fe, B).

, qTbo, o5 Lao, of' When the amorphous ribbon obtained by ultra-quenching is annealed at 627°C, the coercive force becomes 9k.
It was found that Oe can be reached (Br is 5kG). However, in this case, the maximum energy product is low due to the poor squareness of the magnetization curve (N, C, Koon et al. App1. Phys.
s, 1. ett.

38 (10) 1981. pp. 840-842).

Also Kabacoa (L, Kabacoff) 'J is (
It has been reported that ribbons prepared by a-quenching with a composition of 1-zPrx (x-0 to 0.3 atomic ratio) are FeFist Pr two-component systems and have a coercive force at the koe level at room temperature. These ultra-quenched, glued or sputtered thin films are not practical permanent magnets that can be used as such, and practical permanent magnets cannot be obtained from these ribbons or thin films. That is, the conventionally proposed FeBR
A bulk permanent magnet body having arbitrary shape and dimensions cannot be obtained from an RFe-based ribbon or an RFe-based thin film. In addition, the magnetization curves of the FeBR ribbons reported so far have poor squareness (they are not considered to be practical permanent magnet materials that can compete with conventionally used magnets). Moreover, the thin films produced by super-quenching and sputtering are isotropic in nature, and it was virtually impossible to obtain a practical permanent magnet with magnetic anisotropy from them.

The basic purpose of the present invention is to obtain a new permanent magnet material that eliminates the drawbacks of conventional materials, does not necessarily require the use of rare rare earths such as Sm, and does not contain many components that are problematic in terms of resources such as 00. . Furthermore, the present invention has good magnetic properties at room temperature, can be formed into any shape and practical size, has a highly square magnetization curve, and makes effective use of light rare earth elements, which are abundant in resources. The purpose of the present invention is to provide a permanent magnet material and a method for manufacturing the same.

The present inventors conducted intensive research on permanent magnet materials to achieve this purpose, and found that F
A part of e is replaced with Go, and the additive element M, that is, Ml(Ti
, Zr, Hf, Mn, Ni, Ge, Sn,
Bi, Sb) and M2 (V, Nb, Ta, Mo
, W, Cr, AI)
It has been discovered that a permanent magnet material with extremely excellent magnetic properties, particularly coercive force and squareness, can be obtained by molding, sintering, and heat-treating a pair of M-based alloy powders of Jk, , and i. This led to the invention.

That is, according to the present invention, 8 to 30 atoms of R (wherein R is at least one rare earth element including indolium Y), 2 to 2H boron B, and 50 or less co
(excluding exposed Co 0%), predetermined % (n addition element M (
However, M is at least one type of Ml and at least one type of M
2, of which the old is Ti 4.5X or less, Z
r 5.5% or less, Hf 5.5X or less, Mn
8.0% or less, Ni 8.0% or less, Ge 7. OX or less, Sn 3.5X or less, Bi 5.0X or less, and Sb 2.5% or more with T-c, M2 HaV L5% or less, sb 12.5% or more T,
Ta 10.5% or less, No L5'X or less, W
L5$ or less, Cr 8.5% or less, and AI 9.
It is less than 5%.

The total amount of M is the above z of the element contained in Ml and M2.
(The same applies to cases where Ml and M2 each contain two or more elements), and has a composition (FeBRM M1 composition) with the balance consisting of iron and impurities, and has an average particle size of 0. Molding 3-80gm of alloy powder, 9
A FeCoBRM permanent magnet material can be produced by sintering the material at 00-1200'C in a non-oxidizing or reducing atmosphere and heat-treating at 350'C to the sintering temperature. This permanent magnet material is FeC.

When BRM is anisotropic, it exhibits particularly excellent magnetic properties.

The present invention is unique in that, unlike conventional FeBR-based amorphous ribbons, magnetically anisotropic permanent magnets can be obtained, but isotropic ones are also superior to conventional isotropic permanent magnets. You can get something. In the following, the permanent magnet material of the present invention will be explained based on the case of magnetic anisotropy as 7. The coercive force and squareness are improved by adding the element M (Ml, 82) and aging treatment, but in addition, light A1 earths such as Nd and Pr, which are abundant in resources, are added as rare earth elements. It is used to develop high magnetic properties.

Generally, when Go is added to an Fe alloy, the Curie point Tc may rise or fall depending on the increase in the amount added, and it is generally difficult to predict the effect of the addition. In the present invention, it has been revealed that as a result of replacing Fe with Go, Tc gradually increases as the amount of Go substitution increases.

Moreover, a similar tendency is confirmed regardless of the type of R in the magnet material composition. Even if the amount of Go substitution is small (for example, 1%)
Effective for increasing Tc, approximately 310~310 depending on the amount of CO replacement
An alloy with an arbitrary Tc of about 750°C can be obtained or CO
A sufficient effect can be obtained when the amount is 5 oz or less (hereinafter 2 indicates the atomic percentage in the alloy), and Go (if is iHc IkOe
In order to achieve the above, it is set to 50% or less.

B should be 2% or more in order to satisfy the coercive force of 1 kOe or more, and 28% or less in order to make the residual magnetic flux density of the hard ferrite Br about 4 kG or more. The rare earth element R is required to be 8% or more in order to have a coercive force of 1 kOe or more, and is combustible, which makes industrial handling and manufacturing difficult, and is expensive, so it should be 30X or less. Pure poron or ferroboron can be used as B, and AI can be used as impurity.
, Si, C, etc. can be used.

As R, it is possible to use the resource-rich "Xuanko" class 2, and it does not necessarily require 5Ill or mainly Sm, so the raw material is cheap and it is extremely suitable for southern use. The permanent magnet of the present invention is advantageous in terms of both resources and cost compared to conventional R-co magnets, and can provide even more excellent magnetic properties. The rare earth element R used in the present invention is a rare earth element that includes Y, light rare earths, and positive rare earths, and one or more of them is used. That is, this R includes Nd, Pr, La, Ce, Tb,
Dy, Ha, Er, Eu.

Sm, Gd, Pffl, Tm, Yb, Lu and Y are included. Light rare earths are sufficient for R;
Particularly preferred are Nd and Pr. In addition, one type of R is usually sufficient, but for practical use a mixture of two or more types (Mitsuhmetal, Didim, etc.) can be used for reasons such as convenience, and other types such as Sm, Y, La, Ce, Gd, etc. (7) R, 4H: Can be used as a mixture with Nd, Pr, etc.

Note that R does not have to be a pure earth element, and may also be one containing impurities that are unavoidable in production within an industrially available range.

As the alloy powder, an alloy of Fe-C:o-B-R- or a mixture of two or more such alloys can be used. Also,
Heath alloy (Fe-Co-B-R; Fe-Go-B-
R-M), as well as alloys of R and constituent elements, such as R-F
e-Go gold alloy Other basic elements Fe, Co, B,
F! An alloy of M and the additive element M can be used.

In particular, these alloys can be used supplementarily to adjust the composition. The M component can also be used as a single powder, and the other components can also be supplemented with single powders.

In the permanent magnet material of the present invention, the additive element M, particularly M2, has the effect of increasing the coercive force. Increasing the coercive force increases the stability of the magnet and expands its applications. But M
As Br increases, Br decreases, and therefore the maximum energy balance (BH) n+ax decreases. r13H)wa
Recently, there have been many applications that require a high coercive force He even if x is a little lower.
It is useful in two ways.

In order to clarify the effect on Br caused by the addition of each element M, the change in Br was measured by changing the amount of addition, and the range was determined to be equal to or higher than about 4 kG of Br in hard ferrite. The effect of each element of M on Br is as disclosed in Japanese Patent Application No. 58-5813, and as the amount of M added increases, Br decreases almost uniformly except for Bi, Mn, and Ni. Also, (B)I of l\-doferite
)IIlax about 4MG considering the range above about 47GOe M
The upper limit of the amount of Ti added is 4.5% for the old model.
Zr 5.5%, Of 5.52:, Mn 8.0%.

Ni8. OX, Ge 7.0%, Sn 3.5%, Bi 5.0%, and Sb 2.5%, and for M2, V 9.
5%, Nb 12.5%, Ta 10.5%, Mo 9.5%, W 8.
5%, Cr 8.5%, and AI 8.5%.

Ml and M2 can each be added singly or in combination of two or more. In this case, the intermediate value of the characteristics of each additive element is generally indicated, and the content of old and M2 is within the range of the above percentages, and the content is not more than the maximum value of -1-2 for each element.

Within the above FeCoBRM composition range, the maximum energy (BH) wax is a hard ferrite magnet (~4MG
It is equivalent to or higher than Oe).

Moreover, in order to make (BH)wax 7MGOe or more, preferably the composition is as follows. That is, it contains light rare earth elements in an amount of 50% or more of the total R, and contains 11 to 24% of R13.
-27$ c7) B, Go 50% or less (excluding Tadashi CoO%), additive element M1 is Ti 4.0% or less,
Zr 4.5% or less, Hf 4.5% or less, Mn 6.
OX or less, Ni 3.5% or less, Ge 5.5% or less, Sn 2.5% or less, Bi 4.0% or less, and His
b 1.5 Z or less, M21iV 8.0% or less, Nb lo, 5% or less, Ta 9.5% or less, No
7.5% or less, W 7.5% or less, Gr 6.5% or less, and AI 7.5% or less.

The content of old and M2 is less than the atomic percentage of the element having the maximum value among the contained elements of old and M2, and the remainder is substantially within the composition range of Fe.

Furthermore, in order to make (BH)maw 7MGOe or more, the most preferable range is to add light rare earth elements to 50$ or more of the total R.
Contains 12-20% R14-24%
, G.

50% or less ((excluding Ll-1, Co 0%), added elements: Ti 3.5% or less, Zr 3.5% or less, )I
f 3.5% or less, Mn 4.0X or less, Ni 2.
0% or less, Ge4.0z or less, Sn 10% or less, B
i 3.0% or less, SbO, 5% or less, M2 is V6.5z or less, Nb 8.5% or less, T
a 8.5 or less, No 5.5 or less, W 5.5X or less, Cr 4.5 or less and AI 5.5 or less, and the content of old and M2 is based on the content of each of the contained elements of Ml and M2. Of these, the composition having the maximum value is less than or equal to the atomic percentage, and the remainder is substantially within the composition range of Fe. In this case, (BH)f
fiax reaches a maximum energy product of 1 OMGOe or more + 1 ton class height of 33 MGOe or more. The amount of M added is determined by the iHc increasing effect, Sr decreasing tendency, (
BH) If you consider the impact on wax, (BH) maw
0.1 to 3z is most desirable in order to obtain 301j[;

Moreover, the Fe-C:o-BRM alloy of the present invention is Go5
% or more, the temperature coefficient (α) of the residual magnetic flux density (Br) becomes α≦0.1%/°C, and the temperature characteristics are good.
Not only does it have better temperature characteristics than the Fe-B-R alloy that does not contain o, but the fA magnetic convex curve squareness is improved by the addition of Co, so the maximum energy product is improved. At Go below 25%, other magnetic properties (
In particular, the energy product) is substantially not adversely affected. C.

When exceeds 25z, (BH)wax decreases. In addition, Go has more corrosion resistance than Fe, so Fe-B
It is possible to impart corrosion resistance by adding Go to the -R alloy.

The permanent magnet made of the FeCoBRM-based sintered body of the present invention is
The presence of unavoidable impurities in the external industrial production of Fe, Go, B, R, and H cannot be tolerated.

Further, the permanent magnet material of the present invention includes Cu, C, S, P,
(a.

Mg, 0. It is also possible to contain a small amount of Si or the like, making it possible to improve manufacturability and reduce costs. That is, Cu3.
5g or less, S2. Below OE, c 4. Below OX, P
3.5g or less, Ca 4% or less, Mg 4% or less, 02
% or less, Si content of 5% or less (however, the total amount is less than the maximum value of each element) is still more than the same level of Br (about 4 kG) as hard ferrite, and is useful. Cu,
P may be mixed in from inexpensive raw materials, C may be mixed in from organic molding aids, etc., and S may be mixed in during the manufacturing process.

The manufacturing method of the present invention is to press-form the Fe1l;osB*ReM alloy powder having an average particle size of 0.3 to 8. The method is characterized in that sintering is performed at a temperature of 800 to 1200°C (in an atmosphere), and further heat treatment is performed at a temperature range from 350°C to the sintering temperature.

Hereinafter, the manufacturing method of the present invention will be explained in the case of a magnetically anisotropic permanent magnet.

First, the Fe*Co·'s-RM alloy powder is obtained as a starting material. This can be achieved by normal alloy melting and casting.
The alloy pI lump may be crushed and provided by classification, blending, etc., or it may be obtained from the oxide by a reduction method using a reducing agent such as Ca, but the average of FeφCO・BRM alloy powder A particle size of 0.3 to 80 gm is used. If the average particle size exceeds 80 pm, excellent magnetic properties cannot be obtained. When the average particle size is less than 0.3 p, Ia, the oxidation of the powder becomes significant during pulverization and subsequent manufacturing steps, and the density after sintering does not increase, resulting in poor magnetic properties. When the average particle size is in the range of 40 to 80 ILm, the coercive force among the magnetic properties is somewhat low. In order to obtain excellent magnetic properties, the average particle size of the alloy powder is most preferably 1.0 to 20 gm.

It is preferable to grind wetly, using an alcohol solvent,
Hexane, trichloroethane, trichloroethylene xylene, toluene, fluorine-based melt, paraffin-based solvents, etc. can be used.

Next, the alloy powder is shaped. The molding can be carried out in the same manner as the usual powder metallurgy method, preferably pressure molding, and in order to obtain anisotropy, pressing in a magnetic field. For example, alloy powder is heated at 0.5 to 3.0 Ton/in a magnetic field of 5 kQe or more.
A molded body is formed by applying pressure at a pressure of cm'. This pressure molding in a magnetic field can be carried out either by molding the powder as it is or by molding it in an organic solvent such as acetone or l.luene.

Next, this molded body is sintered at a predetermined temperature (900 to 1200°C) in a reducing or non-oxidizing atmosphere. For example, this molded body is placed in a vacuum of 1O-2 Torr or less,
Sintering is performed in an inert gas or reducing gas atmosphere of 1 to 780 Torr and a purity of 9L9$ or higher at a temperature range of 91) 0 to 1200°C for 0.5 to 4 hours. Sintering temperature 900'O
Below this, sufficient sintering density and high remanence density cannot be obtained. Moreover, above 1200° C., the sintered body is deformed and the orientation of the crystal grains is lost, resulting in a decrease in residual magnetic flux agitation and a decrease in the squareness of the demagnetization curve. Also, the sintering time is 5
A sintering time of 0.5 to 4 hours is preferable, but if the sintering time is too long, there will be a problem with delayed production, so in consideration of the reproducibility of the magnetic properties, a sintering time of 0.5 to 4 hours is preferable.

Sintering is carried out in a high vacuum, which is a non-butyricating atmosphere, or in an atmosphere of inert scum or reducing gas, since R, which is a component of this alloy, is extremely easily oxidized at high temperatures. The higher the purity of the reducing gas, the better. 1 to 780 as a method of obtaining high sintered density when using an inert gas.
It is also possible to carry out in a reduced pressure atmosphere of Totr Mineko.

The temperature increase rate during sintering is not particularly specified, but in the case of the wet press method mentioned above, in order to remove the organic solvent, the temperature is increased at a rate of 30 °C/+a in or less, or during the temperature increase. It is desirable to remove the solvent by holding the temperature in a temperature range of 200 to 800°C for about 1 hour or more.

After sintering, the cooling rate to room temperature is preferably 3θ'C/lll1n or more in order to reduce product variation, and the cooling rate is 150°C/min in order to improve the magnetic properties by subsequent heat treatment (aging treatment). This is preferable (
However, it is also possible to immediately enter a heat treatment step following sintering. ). Preferably, after sintering, it is cooled to a temperature of 800"C or less at a rate of 100"C/min or more. Thereafter, aging treatment may be performed continuously, or aging treatment may be performed by cooling to room temperature and then reheating.

The aging treatment is performed in a vacuum, inert gas, or reducing gas atmosphere at a temperature range from 350°C to below the sintering temperature for approximately 5 minutes to "tovf".The aging treatment atmosphere is such that the main component R in the alloy is Since it reacts rapidly with oxygen or moisture at high temperatures, it is desirable that the degree of vacuum be less than IQ Torr in the case of a vacuum, and that the purity of the atmosphere be 99.99% or more in the case of an inert gas or reducing gas atmosphere.

The optimum sintering temperature of the alloy of the present invention varies depending on the composition, and the aging treatment must be performed at a temperature below each sintering temperature of the magnet material of the present invention. for example? 1Fe5C: o8B14NdlTilW alloy, 52Fe25Go5B17NdO, 5Mn0.5AI
For alloys, the upper limit temperature for aging treatment is 350°C 1100°C.
It is 0°C. Generally, the two-time aging treatment temperature can be increased for compositions that are rich in Fe, low in B, or low in R. However, if the aging temperature is too high, the crystal grains of the alloy of the present invention will grow excessively, and the magnetic properties, especially the coercive force, will be low.
At the same time, the optimal aging treatment time becomes extremely short, making it difficult to control manufacturing conditions, making it impractical. Further, if the temperature is lower than 350° C., the aging treatment takes an extremely long time, which is impractical, and the squareness of the aging curve deteriorates, making it impossible to obtain an excellent permanent magnet. In order to practically obtain excellent magnetic properties without causing excessive growth of crystal grains in the permanent magnet material of the present invention, the aging treatment temperature is most preferably 450°C to 800°C, and more preferably 500°C to 700°C. It is °C. The aging treatment is performed for 5 minutes to 70 hours, but if the aging treatment time is less than 5 minutes, the effect of the aging treatment will hardly appear, and the obtained magnetic 11 characteristics will have a large fluctuation.

- If the force and aging treatment time exceeds 0 hours, it is difficult to say that it is practical because it takes too long a time.In order to obtain excellent magnetic properties with good reproducibility, the aging treatment time must be 3.
Preferably 0 minutes to 8 hours. It is desirable that the aging treatment be performed in a substantially isothermal state.

In addition, multi-stage aging treatment of two to seven stages is also effective as a method for aging the present magnetic alloy, and the first stage can be set at 800°C or higher, and the second stage and subsequent stages can be set at 800°C or lower. For example 11
88Fe-5Go-78-18Nd- sintered at 00℃
For 1Ge-INb alloy, the temperature is 800°C to 850°C as the first stage.
After the first stage aging treatment for 30 minutes to 8 hours at a temperature range of 30°C, the second stage and subsequent stages are aged at least once at a temperature range of 400 to 800°C for 2 hours to 70 hours to remove residual A crushed magnet characteristic with high magnetic flux amplitude, coercive force, and squareness of the demagnetization curve can be obtained. In particular, the aging treatment after the second stage is effective in dramatically improving coercive force. In addition, as a separate method of aging treatment, instead of multi-stage aging treatment, cooling may be performed at a constant cooling rate in the temperature range of 350°C to 950°C using a cooling method such as air cooling or water cooling during aging treatment. However, the cooling rate at that time is 0.2℃/11n to 2
It is necessary that the temperature is 0°C/win. These aging treatments may be performed as is after sintering, or may be performed after sintering by cooling to room temperature and then raising the temperature again.

Further, the manufacturing method of the present invention can be applied not only to magnetically anisotropic permanent magnets but also to isotropic permanent magnets. In addition, in the method for manufacturing isotropic permanent magnets, the alloy powder is molded without being placed in a magnetic field, and other steps can be used as is.

In the case of isotropy, R10-25%, 83-23%
, (BH)mat 2 in a composition consisting of 50% or less CO1, a predetermined 2 M, the balance Fe and unavoidable impurities.
MGOe or more can be obtained. Isotropic magnets originally have low magnetic properties of 1/4 to 176 that of anisotropic magnets, but according to the present invention, they nevertheless have high properties that are extremely useful as isotropic magnets. is obtained.

In the case of isotropy, iHc increases as the R amount increases, but Or decreases after reaching its maximum value. Thus (BH
)may 2MGOe or more, the Ri is 10% or more and 25% or less.

Further, as Bi increases, iHc increases, but Br decreases after reaching its maximum value. Thus (8) 1) wax2MG
To obtain Oe or higher, it must be in the range of 83-23%.

Preferably, the main components of R (all R medium light, ffi
Earth is 50 atoms 2 or more) and 12-20% R15-1
With a composition of 82 B and the remainder F'e (B) I) wax 4M
It exhibits the second highest magnetic properties than GOe. The most preferred range is Nd.

Light rare earth such as Pr is the main component of R, and R1 is 12 to 18%.
For a composition of 6 to 18% B balance Fe, (BH)mat is 7
With 8GOe or higher, properties never seen before with isotropic permanent Ia6 can be obtained.

As for Ml, it is best to keep it in the same range as in the case of anisotropy except for the following (Ti: 4.7% or less, Ni: 4.7% or less.

Ge 8. OX or less). For M2, it is better to have the same range as the anisotropy except for the following. (V 10.5% or less, W 8
．． (8% less). When both old components are isotropic, Br shows a decreasing tendency as the amount added increases, and Br 3kG
Above (isotropic hard ferrite (7) (BH) may
2MGOe's formula) is shown within this range.

In the case of anisotropic magnets, binders and lubricants are generally not needed as they interfere with the orientation during molding, but in the case of isotropic magnets, they contain binders and lubricants to make it easier to press. Improving efficiency, increasing the strength of the molded body, etc. are possibilities.

Even in the case of isotropy, the presence of impurities that are unavoidable in industrial production can be tolerated. That is, in addition to R, B, and Fe, within a certain range G,
P, S, Cu, Ca, 111g, O,S
It is also possible to contain i, C4.0% or less, R3.3
% or more [-152.5% or less, Cu 3.3% or less, Ca
4% or less, Mg 4% or less, 02% or less, Si
The total of these is less than 5%.

It is practical if the maximum value or less of each component is used.

As stated in the second part of this article, the permanent magnet material and the method for producing the same of the present invention produce a new Fe*Co・BRM-based permanent magnet that exhibits excellent magnetic properties with high coercive force and high energy product. This is what we provide. Also, as R, Nd, Pr
By using light rare earth elements such as, it is a permanent magnet that is excellent in terms of resources and cost, and has high industrial applicability.

Hereinafter, aspects and effects of the present invention will be further explained according to examples. (The IJL examples and described aspects are not intended to limit the invention.

Tables 1 to 4 show various Fea produced by the following steps.
The characteristics of a water-immersed magnet body having a Ca・B・RM system composition are shown.

(1) The starting materials are electrolytic iron with a purity of 1] 9.9% (equal amount %, hereinafter the same applies to the purity of raw wood) as Fe, B and siteferroporon alloy (19.38% B, 5.32%)
A.I.

0.74% Si, 0.03% G, balance Fe),
R,! l: Uses Shite pure JFQ 99% or more (impurities are mainly other earth metals).

As for CO, 98.8% purity carbon fisC:o was used. The old ones were 99% pure Ti, AI, Mn, Sb.
, Ni, Sn.

Ge, 95% Hf, and Z [7.5% Toshita]
Ferrozirconium containing Zr was used.

M2 Toshite has a purity of 99"X Ta, 9B'X tvW,
98,92 AI, ferrovanadium containing 81.2% V as V, ferronniobium containing 87.6% Nb as Nb, and ferrochrome containing 81.9% C as Cr.

(2) Magnet raw materials were melted using high frequency induction. At that time, an alumina crucible was used as the crucible, and an ingot cast into a water-cooled copper mold was used.

(3) Crush the ingot obtained by melting to 35 mes
After this, the powder was further pulverized using a ball mill to obtain particles having a predetermined average particle size.

(4) The powder was molded under a predetermined pressure in a magnetic field (however, when manufacturing isotropic magnets, molding was performed without applying a magnetic field).
,.

(5) The molded body was sintered in a predetermined atmosphere within the range of 800 to 1200°C, and then subjected to a predetermined heat treatment.

Example 1 Atomic percentage composition 61Fe 1OCo 7B 16Nd
2MO・IN+ alloy powder with average particle size of 3μ fat is 1
After pressure molding in a 5 kOe magnetic field at a pressure of 1.57 on/am', sintering was performed at 1120°C in 350 Torr Ar with H,H% purity at a cooling rate of 60° after sintering.
Cooled to room temperature at 0°C/win. Furthermore, aging treatment was performed at 800° C. for 20 minutes, 120 minutes, 240 minutes, and 3000 minutes to obtain a magnet according to the present invention. Magnet property results and temperature coefficient α (%/'C) of residual magnetic flux density (Br) of this alloy magnet
) are shown in Table 1 along with comparative examples (after sintering).

Table 1 Example 2 j5: (%-N composition 55Fe-18Co-10B-
45Nd-2Y-2Nb-IGe, #1 degree 3gm
An alloy powder of I, OT in a 15k13e magnetic field
After pressure molding at a pressure of a n/cm'.

H, H9% &! 11 in 700 Tarr Ar of degrees
Sintered at 90°C for 14 hours, cooled at 350°C after sintering
#++in to cool to room temperature. Another 3 x 10”
Aging treatment was performed in a Torr vacuum at each temperature shown in Table 2 for 2 hours to obtain a magnet of the present invention. The magnet characteristic results and the temperature coefficient α (z/°C) of the residual magnetic flux density (Br) are shown in Table 2 together with comparative examples (after sintering, etc.).

Table 2 Example 3 Fe-Co-BRM alloy powder having an average particle size of 2 to 15 gm and the atomic percentage composition shown in Table 3 was heated to 15 kOer.
b After pressure molding in a magnetic field at a pressure of 1.5 Ton/crrf, 99.99B2 purity (1) 20OTorr A
The material was sintered at 1120° C. for 12 hours at a temperature of 1,120° C., and after sintering, it was rapidly cooled to room temperature at a cooling rate of 700° C./+nin. 4 more
Aging treatment in Ar at 00 Torr at 700°C for 2 hours.
The magnet of the present invention was obtained by carrying out the test for several hours. The magnetic properties and the temperature coefficient α (X/°O) of Br are shown in Table 3 along with a comparative example that does not have 6 Go.

Example 4 F having the following atomic percentage composition having an average particle size of 1 to 10 gm
1. e-Go-B-R-8 alloy powder in no magnetic field. OTo
After pressure molding at a pressure of n/crrf, 99.99%
Sintering was carried out at 1100° C. for 2 hours in 200 Torr Ar of purity, and after sintering, it was rapidly cooled to room temperature at a cooling rate of 600’c/win.

Furthermore, aging treatment was performed in 500 Tart Ar for 600 hr.
C. for 2 hours to obtain a magnet of the present invention. The results of the magnetic properties are shown in Table 4 together with the sample after sintering without aging treatment (comparative example).

Table 4

Claims (2)

[Claims] (1) 8 to 30% R in atomic percentage (R is at least one of the rare earth elements including indolium Y)
, 2-28% Not, B, 50 X or less ty) cO
(However, excluding Co Ox), M of prescribed 2 (However, M
consists of at least one type of old and at least one type of M2, of which the old is Ti 4.5X or less, Zr 5.5% or less, H
f 5.5% or less, Kn 8.0% or less, Ni 8.
0% JJ, -t, Ge 7.0% or less, Sn 3
．． 5% or less, Bi 5.0% or less, and Sb
2.5% or less, and M2HaV 9.5XuT,
Nb 12.5% or less, Ta 10.5% or more,
MO9.5% or less, 'W L5X or less, Cr 8.5
% or less, and AI 3.5% or less, and the total of M is less than or equal to the maximum of the two percentage values of the element containing Old and M2, and for elements where Old and M2 are each 2 or more. ) and the balance is iron (Fe) and impurities with an average particle size of 0.3 to 80 ILm, and
A permanent magnet material obtained by sintering this molded body at 900 to 1200°C and heat treating this sintered body at 350°C to below the sintering temperature. (2) 8 to 30% R in atomic percentage (R is at least one rare earth element including yttrium Y), 2
~28% boron B, 502 or less c. (7': Excluding LCo OX), predetermined % (1') MC
The f-knee LM consists of at least one type of old and at least one type of 2, of which the old is Ti 4.5% or less, Zr 5.5X or less, H
f 5.5% or less, Mn 8.0 or less, Ni 8.0% or less.
0% or less, Ge 7. OX or less, Sn 3.5% or less, Bi 5.0'X or less, and Sb 2.5% or less, and M2V 9.5% or less, Nb 12.
5% or less, Ta 10.5% or less, No. 9.
5% or less, W 8.5X or less, Cr 8.5% or less,
and AI 9.5% or less, and the total amount of M is less than or equal to the maximum of the above values of the elements contained in Ml and M2, even if Ml and M2 each contain two or more elements. ), and the balance is Fe and impurities, forming an alloy powder with an average particle size of 0.3 to 8 (J) ttn.
A step of sintering at 0 to 1200°C, and then 3
A method for producing a permanent magnet material, comprising a step of heat treatment at 50°C or below the sintering temperature.